Photographic products and processes employing novel nondiffusible bridged azoaminophenol magenta dye-releasing compounds and precursors thereof

ABSTRACT

Photographic elements, diffusion transfer assemblages and processes are described which employ a novel nondiffusible compound having a releasable, bridged, azoaminophenol magenta dye moiety or precursor thereof having the formula: ##STR1## wherein: (a) R represents hydrogen, a hydrolyzable moiety or CAR; 
     (b) R 1  represents hydrogen; 
     (c) R 2  represents an alkyl group of 1 to about 6 carbon atoms or CAR; or R 1  and R 2  represent an alkylene group which can be taken together with the atoms to which they are attached to complete a 5- or 6-membered heterocyclic ring; 
     (d) R 3  represents an alkyl group of 1 to about 6 carbon atoms or CAR; 
     (e) R 4  represents hydrogen; or R 3  and R 4  represent an alkylene group which can be taken together with the atoms to which they are attached to complete a 5- or 6-membered heterocyclic ring; 
     with the proviso that at least one of the 5- or 6-membered heterocyclic rings of (c) or (e) is present in the compound; 
     (f) CAR represents a ballasted carrier moiety capable of releasing the diffusible magenta dye moiety or precursor thereof under alkaline conditions; and 
     (g) n is 0, 1 or 2, with the proviso that when n is 0, then at least one of R, R 2  or R 3  is CAR.

This is a division of application Ser. No. 282,613, filed July 13, 1981.

This invention relates to photography and more particularly to colordiffusion transfer photography employing certain nondiffusible azodye-releasing compounds which, as a function of development of a silverhalide emulsion layer, release a diffusible metallizable, bridged,azoaminophenol magenta dye or precursor thereof. Highly stable metalcomplexes of this dye are formed during processing.

U.S. Pat. No. 4,142,891 of Baigrie et al relates to variousnondiffusible azo dye-releasing compounds. It would be desirable toprovide compounds with improved properties over those of Baigrie et al,such as better hue, less unwanted absorption, and narrower bandwidths.

U.S. Pat. Nos. 2,864,813, 3,051,697 and 3,118,871 relates to various4-azoaniline dyes. These dyes, however, do not have chelating groups,carrier moieties, or the bridged, azoaminophenol ring structure of thecompounds described herein. There is also no disclosure that thesecompounds could be used in photographic elements.

It would be desirable to provide improved dye-releasing compoundscontaining chelating dye moieties, so that the dye which is releasedimagewise during processing can diffuse rapidly to an image-receivinglayer containing metal ions to form a metal-complexed, dye transferimage in a short amount of time which has better hues, less unwantedabsorption and narrower bandwidths, than those of the prior art, as wellas good stability to heat, light and chemical reagents.

A photographic element in accordance with the invention comprises asupport having thereon at least one photosensitive silver halideemulsion layer, the emulsion layer having associated therewith a dyeimage-providing material comprising a nondiffusible compound having areleasable, bridged, azoaminophenol magenta dye moiety or precursorthereof, the compound having the formula: ##STR2## wherein: (a) Rrepresents hydrogen, a hydrolyzable moiety or CAR;

(b) R¹ represents hydrogen;

(c) R² represents an alkyl (including substituted alkyl) group of 1 toabout 6 carbon atoms or CAR; or R¹ and R² represent an alkylene groupwhich can be taken together with the atoms to which they are attached tocomplete a 5- or 6-membered heterocyclic ring;

(d) R³ represents an alkyl (including substituted alkyl) group of 1 toabout 6 carbon atoms or CAR;

(e) R⁴ represents hydrogen; or R³ and R⁴ represent an alkylene groupwhich can be taken together the atoms to which they are attached tocomplete a 5- or 6-membered heterocyclic ring;

with the proviso that at least one of said 5- or 6-membered heterocyclicrings of (c) or (e) is present in the compound;

(f) CAR represents a ballasted carrier moiety capable of releasing thediffusible magenta dye moiety or precursor thereof under alkalineconditions, e.g., as a function of development of the silver halideemulsion layer; and

(g) n is 0, 1 or 2, with the proviso that when n is 0, then at least oneof R, R² or R³ is CAR.

In the above formula, the alkyl or substituted alkyl groups which R² andR³ represent can be, for example, methyl, ethyl, propyl, isopropyl,cyanoethyl, sulfamoylpropyl or ethoxycarbonylmethyl.

In the above formula, R¹ and R² and/or R³ and R⁴ can represent a 5- or6-membered heterocyclic ring which, when taken together with its fusedbenzene ring, forms a julolidine, lilolidine,1,2,3,4-tetrahydroquinoline or indoline ring system.

In a preferred embodiment of the invention, R represents hydrogen, R¹and R² complete a 6-membered heterocyclic ring, R³ and R⁴ complete a6-membered heterocyclic ring and n is 1. In another preferredembodiment, R represents hydrogen, R¹ and R² complete a 6-memberedheterocyclic ring, R³ represents methyl, R⁴ represents hydrogen and nis 1. In yet another preferred embodiment, R and R¹ each representshydrogen, R² represents methyl, R³ and R⁴ complete a 5-memberedheterocyclic ring and n is 1.

Other substituents may also be present in the two rings illustratedabove, such as alkyl of 1 to 6 carbon atoms, alkoxy, halogens, andsolubilizing groups such as sulfonamido, sulfamoyl, phenylsulfamoyl,carboxy, sulfo or hydrolyzable precursors thereof.

In another embodiment of the invention, CAR may have attached theretotwo azo dye moieties, as shown by the formula above, in which case twodye moieties will be released from one CAR moiety.

As stated above, R represents hydrogen, a hydrolyzable moiety or CAR.Hydrolyzable moieties which can be employed in our invention includeesters such as acetate, benzoate, pivalate, carbamates, imidomethylgroups as described in Reczek and Welter, U.S. application Ser. No.220,408, filed Dec. 29, 1980, or any of the blocking groups which can becleaved by an intramolecular nucleophilic displacement reaction, asdisclosed in Mooberry and Archie U.S. Ser. No. 949,462, filed Oct. 10,1978, the disclosure of which is hereby incorporated by reference.

There is great latitude in selecting a CAR moiety which is attached tothe dye-releasing compounds described above. Depending upon the natureof the ballasted carrier selected, various groups may be needed toattach or link the carrier moiety to the dye. Such linking groups areconsidered to be a part of the CAR moiety in the above definition. Itshould also be noted that, when the dye moiety is released from thecompound, cleavage may take place in such a position that part or all ofthe linking group, if one is present, and even part of the ballastedcarrier moiety, may be transferred to the image-receiving layer, alongwith the dye moiety. In any event, the dye nucleus as shown above can bethought of as the minimum which is transferred.

CAR moieties useful in the invention are described in U.S. Pat. Nos.3,227,550; 3,628,952; 3,227,552 and 3,844,785 (dye released bychromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dyereleased by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No.3,728,113 (dye released from a hydroquinonylmethyl quaternary salt);U.S. Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release);British Patent Publication No. 2,017,950A (dye released by a dye bleachprocess); U.S. Pat. Nos. 4,053,312; 4,198,235; 4,179,231; 4,055,428 and4,149,892 (dye released by oxidation and deamidation); and U.S. Pat.Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607; British Pat.No. 1,464,104; Research Disclosure 14447, April 1976; and U.S. Pat. No.4,139,379 of Chasman et al (dye released by miscellaneous mechanisms),the disclosures of which are hereby incorporated by reference.

In a further preferred embodiment of the invention, the ballastedcarrier moiety or CAR as described above may be represented by thefollowing formula:

    (Ballast-Carrier-Link)-

wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration as to render said compound nondiffusible in saidphotographic element during development in an alkaline processingcomposition;

(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety(see "The Theory of the Photographic Process", by C. E. K. Mees and T.H. James, Third Edition, 1966, pages 282 to 283), e.g., moietiescontaining atoms according to the following configuration:

    a (--C═C).sub.b --

wherein:

b is a positive integer of 1 to 2; and

a represents the radicals OH, SH, NH-- or hydrolyzable precursorsthereof; and

(c) Link represents a group which, upon oxidation of said Carriermoiety, is capable of being hydrolytically cleaved to release thediffusible azo dye. For example, Link may be the following groups:##STR3## wherein * represents the position of attachment to Carrier.

The Ballast group in the above formula is not critical, so long as itconfers nondiffusibility to the compound. Typical Ballast groups includelong-chain alkyl radicals, as well as aromatic radicals of the benzeneand naphthalene series linked to the compound. Useful Ballast groupsgenerally have at least 8 carbon compounds, such as substituted orunsubstituted alkyl groups of 8 to 22 carbon atoms; a carbamoyl radicalhaving 8 to 30 carbon atoms, such as --CONH(CH₂)₄ --O--C₆ H₃ (C₅ H₁₁)₂,or --CON(C₁₂ H₂₅)₂ ; or a keto radical having 8 to 30 carbon atoms, suchas --CO--C₁₇ H₃₅ or --CO--C₆ H₄ (t--C₁₂ H₂₅).

For specific examples of Ballast-Carrier moieties useful as the CARmoiety in this invention, reference is made to the November 1976 editionof Research Disclosure, pages 68 through 74, and the April 1977 editionof Research Disclosure, pages 32 through 39, the disclosures of whichare hereby incorporated by reference.

In a highly preferred embodiment of the invention, the ballasted carriermoiety or CAR in the above formula is a group having the formula:##STR4## wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration (e.g., simple organic groups or polymeric groups) as torender said compound nondiffusible in a photographic element duringdevelopment in an alkaline processing composition;

(b) D is OR⁵ or NHR⁶ wherein R⁵ is hydrogen or a hydrolyzable moiety,such as acetyl, mono-, di- or trichloroacetyl radicals, perfluoroacyl,pyruvyl, alkoxyacyl, nitrobenzyl, cyanobenzoyl, sulfonyl or sulfinyl,and R⁶ is hydrogen or a substituted or unsubstituted alkyl group of 1 to22 carbon atoms, such as methyl, ethyl, hydroxyethyl, propyl, butyl,secondary butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclobutyl,4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl, benzylor phenethyl (when R⁶ is an alkyl group of greater than 8 carbon atoms,it can serve as a partial or sole Ballast);

(c) Y represents at least the atoms necessary to complete a benzenenucleus, a naphthalene nucleus, or a 5- to 7-membered heterocyclic ring,such as pyrazolone or pyrimidine; and

(d) j is a positive integer of 1 to 2 and is 2 when D is OR⁵ or when R⁶is hydrogen or an alkyl group of less than 8 carbon atoms.

Especially good results are obtained in the above formula when D is OH,j is 2, and Y is a naphthalene nucleus.

Examples of the CAR moiety in this highly preferred embodiment aredisclosed in U.S. Pat. Nos. 4,076,529; 3,993,638 and 3,928,312, thedisclosures of which are hereby incorporated by reference, and includethe following: ##STR5##

In another highly preferred embodiment of the invention, the ballastedcarrier moiety or CAR in the above formulas is such that the diffusibleazo dye is released as an inverse function of development of the silverhalide emulsion layer under alkaline conditions. This is ordinarilyreferred to as positive-working dye-release chemistry. In one of theseembodiments, the ballasted carrier moiety or CAR in the above formulasmay be a group having the formula: ##STR6## wherein: Ballast is anorganic ballasting radical of such molecular size and configuration asto render said compound nondiffusible in a photographic element duringdevelopment in an alkaline processing composition;

W² represents at least the atoms necessary to complete a benzene nucleus(including various substituents thereon); and

R⁸ is an alkyl (including substituted alkyl) radical having 1 to about 4carbon atoms.

Examples of the CAR moiety in this formula (I) include the following:##STR7##

In a second embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR8## wherein: Ballast isan organic ballasting radical of such molecular size and configurationas to render said compound nondiffusible in a photographic elementduring development in an alkaline processing composition;

W¹ represents at least the atoms necessary to complete a quinone nucleus(including various substituents thereon);

r is a positive integer of 1 or 2;

R⁷ is an alkyl (including substituted alkyl) radical having 1 to about40 carbon atoms or an aryl (including substituted aryl) radical having 6to about 40 carbon atoms; and

k is a positive integer of 1 to 2 and is 2 when R⁶ is a radical of lessthan 8 carbon atoms.

Examples of the CAR moiety in this formula (II) include the following:##STR9##

In using the compounds in formulas I and II above, they are employed ina photographic element similar to the other nondiffusible dye-releasersdescribed previously. Upon reduction of the compound as a function ofsilver halide development under alkaline conditions, the metallizableazo dye is released. In this embodiment, conventional negative-workingsilver halide emulsions, as well as direct-positive emulsions, can beemployed. For further details concerning these particular CAR moieties,including synthesis details, reference is made to U.S. Pat. No.4,139,379 of Chasman et al, the disclosure of which is herebyincorporated by reference.

In a third embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR10## wherein: Ballast,W² and R⁸ are as defined for formula (I) above.

Examples of the CAR moiety in this formula (III) include the following:##STR11##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 4,199,354 ofHinshaw et al, the disclosure of which is hereby incorporated byreference.

In a fourth embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR12## wherein: Ballast,r, R⁷ and k are as defined for formula (II) above;

W² is as defined for formula (I) above; and

K is OH or a hydrolyzable precursor thereof.

Examples of the CAR moiety in this formula (IV) include the following:##STR13##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 3,980,479 ofFields et al, the disclosure of which is hereby incorporated byreference.

Representative compounds included within the scope of the inventioninclude the following: ##STR14##

A process for producing a photographic transfer image in color accordingto the invention comprises:

(a) treating an imagewise-exposed photographic element as describedabove with an alkaline processing composition in the presence of asilver halide developing agent to effect development of each of theexposed silver halide emulsion layers;

(b) the dye-releasing compound then releasing the diffusible azo dye asdescribed above imagewise as a function of the development of each ofthe silver halide emulsion layers;

(c) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(d) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

The tridentate azo dye ligand which is released from the dye-releasingcompounds in accordance with the present invention will form acoordination complex in the image-receiving layer with polyvalent metalions. The metal ions can be present in the image-receiving layer itselfor in a layer adjacent thereto, or the image-receiving layer can becontacted with metal ions in a bath after diffusion of the dye has takenplace. Metal ions most useful in the invention are those which areessentially colorless when incorporated into the image-receivingelement, are inert with respect to the silver halide layers, reactreadily with the released dye to form a complex of the desired hue, aretightly coordinated to the dye in the complex, have a stable oxidationstate, and form a dye complex which is stable to heat, light andchemical reagents. In general, good results are obtained with polyvalentmetal ions such as copper (II), zinc (II), nickel (II), platinum (II),palladium (II) and cobalt (II) ions.

For example, it is believed that the coordination complex which isformed from the tridentate azo dye ligand according to the invention inone of the preferred embodiments thereof has the following structure:##STR15## wherein: (a) R¹ represents hydrogen;

(b) R² represents an alkyl group of 1 to about 6 carbon atoms; or

R¹ and R² represent an alkylene group which can be taken together withthe atoms to which they are attached to complete a 5- or 6-memberedheterocyclic ring;

(c) R³ represents an alkyl group of 1 to about 6 carbon atoms;

(d) R⁴ represents hydrogen; or

R³ and R⁴ represent an alkylene group which can be taken together withthe atoms to which they are attached to complete a 5- or 6-memberedheterocyclic ring;

with the proviso that at least one of the 5- or 6-membered heterocyclicrings is present in the complex;

Me is metal; and

Lig is one or more ligand groups, depending upon the coordination numberof the metal ion, such as H₂ O, Cl or pyridine, or a second dye moiety.

Thus, in accordance with this preferred embodiment of the invention, aphotographic element is provided which comprises a support havingthereon a coordination complex of a polyvalent metal ion and a compoundhaving the formula: ##STR16## wherein: R¹, R², R³ and R⁴ are asdescribed above.

The element usually contains a photographic mordant or image-receivinglayer to bind the dye or coordination complex thereto. The structuresshown above may also, of course, be substituted in the same manner asdescribed above for the starting compounds from which they are released.

It will be appreciated that, after processing the photographic elementdescribed above, there remains in it after transfer has taken place animagewise distribution of azo dye in addition to developed silver. Acolor image comprising residual nondiffusible compound is obtained inthis element if the residual silver and silver halide are removed by anyconventional manner well known to those skilled in the photographic art,such as a bleach bath, followed by a fix bath, a bleach-fix bath, etc.Such a retained dye image should normally be treated with metal ions tometallize the dyes to increase their light fastness and shift theirspectral absorption to the intended region. The imagewise distributionof azo dye may also diffuse out of the element into these baths, ifdesired, rather than to an image-receiving element. If anegative-working silver halide emulsion is employed in certain preferredphotosensitive elements, described above, then a positive color image,such as a reflection print, a color transparency or motion picture film,is produced in this manner. If a direct-positive silver halide emulsionis employed in such photosensitive elements, then a negative color imageis produced.

The photographic element in the above-described process can be treatedin any manner with an alkaline processing composition to effect orinitiate development. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in thisinvention contains the developing agent for development, although thecomposition could also just be an alkaline solution where the developeris incorporated in the photographic element, image-receiving element orprocess sheet, in which case the salkaline solution serves to activatethe incorporated developer.

A photographic film unit or assemblage in accordance with this inventionis adapted to be processed by an alkaline processing composition, andcomprises:

(1) a photographic element as described above; and

(2) a dye image-receiving layer.

In this embodiment, the processing composition may be inserted into thefilm unit, such as by interjecting processing solution withcommunicating members similar to hypodermic syringes which are attachedeither to a camera or camera cartridge. The processing composition canalso be applied by means of a swab or by dipping in a bath, if sodesired. Another method of applying processing composition to a filmassemblage which can be used in our invention is the liquid spreadingmeans described in U.S. Application Ser. No. 143,230 of Columbus, filedApr. 24, 1980.

In a preferred embodiment of the invention, the assemblage itselfcontains the alkaline processing composition and means containing samefor discharge within the film unit. There can be employed, for example,a rupturable container which is adapted to be positioned duringprocessing of the film unit so that a compressive force applied to thecontainer by pressure-applying members, such as would be found in acamera designed for in-camera processing, will effect a discharge of thecontainer's contents within the film unit.

In the embodiment described above, the dye image-receiving layer mayitself contain metal ions or the metal ions may be present in anadjacent layer, so that the tridentate azo dye ligand which is releasedwill form a coordination complex therewith. The dye thus becomesimmobilized in the dye image-receiving layer and metallized at the sametime. Alternatively, the dye image in the dye image-receiving layer maybe treated with a solution containing metal ions to effectmetallization. The formation of the coordination complex shifts theabsorption of the dye to the desired hue, usually to longer wavelengths,which have a different absorption than that of the initial dye-releasingcompound. If this shift is large enough, then the dye-releasing compoundmay be incorporated in a silver halide emulsion layer without adverselyaffecting its sensitivity.

The dye image-receiving layer in the above-described film assemblage isoptionally located on a separate support adapted to be superposed on thephotographic element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in U.S. Pat. No.3,362,819. When the means for discharging the processing composition isa rupturable container, it is usually positioned in relation to thephotographic element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as would be found in a typical camera used for in-cameraprocessing, will effect a discharge of the container's contents betweenthe image-receiving element and the outermost layer of the photographicelement. After processing, the dye image-receiving element is separatedfrom the photographic element.

In another embodiment, the dye image-receiving layer in theabove-described film assemblage is integral with the photographicelement and is located between the support and the lowermostphotosensitive silver halide emulsion layer. One useful format forintegral receiver-negative photographic elements is disclosed in BelgianPat. No. 757,960. In such an embodiment, the support for thephotographic element is transparent and is coated with animage-receiving layer, a substantially opaque light-reflective layer,e.g., TiO₂, and then the photosensitive layer or layers described above.After exposure of the photographic element, a rupturable containercontaining an alkaline processing composition and an opaque processsheet are brought into superposed position. Pressure-applying members inthe camera rupture the container and spread processing composition overthe photographic element as the film unit is withdrawn from the camera.The processing composition develops each exposed silver halide emulsionlayer and dye images are formed as a function of development whichdiffuse to the image-receiving layer to provide a positive,right-reading image which is viewed through the transparent support onthe opaque reflecting layer background. For other details concerning theformat of this particular integral film unit, reference is made to theabove-mentioned Belgian Pat. No. 757,960.

Another format for integral negative-receiver photographic elements inwhich the present invention is employed is disclosed in Canadian Pat.No. 928,559. In this embodiment, the support for the photographicelement is transparent and is coated with the image-receiving layer, asubstantially opaque, light-reflective layer and the photosensitivelayer or layers described above. A rupturable container containing analkaline processing composition and an opacifier is positioned adjacentthe top layer and a transparent top sheet which has thereon aneutralizing layer and a timing layer. The film unit is placed in acamera, exposed through the transparent top sheet and then passedthrough a pair of pressure-applying members in the camera as it is beingremoved therefrom. The pressure-applying members rupture the containerand spread processing composition and opacifier over the negativeportion of the film unit to render it light-insensitive. The processingcomposition develops each silver halide layer and dye images are formedas a result of development which diffuse to the image-receiving layer toprovide a positive, right-reading image which is viewed through thetransparent support on the opaque reflecting layer background. Forfurther details concerning the format of this particular integral filmunit, reference is made to the above-mentioned Canadian Pat. No.928,559.

Still other useful integral formats in which this invention can beemployed are described in U.S. Pat. Nos. 3,415,644; 3,415,645;3,415,646; 3,647,437 and 3,635,707. In most of these formats, aphotosensitive silver halide emulsion is coated on an opaque support anda dye image-receiving layer is located on a separate transparent supportsuperposed over the layer outermost from the opaque support. Inaddition, this transparent support also preferably contains aneutralizing layer and a timing layer underneath the dye image-receivinglayer.

In another embodiment of the invention, a neutralizing layer and timinglayer are located underneath the photosensitive layer or layers. In thatembodiment, the photographic element would comprise a support havingthereon, in sequence, a neutralizing layer, a timing layer and at leastone photosensitive silver halide emulsion layer having associatedtherewith a dye-releasing compound as described above. A dyeimage-receiving layer as described above would be provided on a secondsupport with the processing composition being applied therebetween. Thisformat could either be integral or peel-apart as described above.

Another embodiment of the invention uses the image-reversing techniquedisclosed in British Pat. No. 904,364, page 19, lines 1 through 41. Inthis process, the dye-releasing compounds are used in combination withphysical development nuclei in a nuclei layer contiguous to thephotosensitive silver halide emulsion layer. The film unit contains asilver halide solvent, preferably in a rupturable container with thealkaline processing composition.

The film unit or assembly used in the present invention is used toproduce positive images in single or multicolors. In a three-colorsystem, each silver halide emulsion layer of the film assembly will haveassociated therewith a dye-releasing compound which releases a dyepossessing a predominant spectral absorption within the region of thevisible spectrum to which said silver halide emulsion is sensitive(initially or after forming the coordination complex), i.e., theblue-sensitive silver halide emulsion layer will have a yellow oryellow-forming dye-releaser associated therewith, the green-sensitivesilver halide emulsion layer will have the magenta or magenta-formingdye-releaser of the invention associated therewith, and thered-sensitive silver halide emulsion layer will have a cyan orcyan-forming dye-releaser associated therewith. The dye-releaserassociated with each silver halide emulsion layer is contained either inthe silver halide emulsion layer itself or in a layer contiguous to thesilver halide emulsion layer.

The concentration of the dye-releasing compounds that are employed inthe present invention may be varied over a wide range, depending uponthe particular compound employed and the results which are desired. Forexample, the dye-releasers of the present invention may be coated inlayers at a concentration of about 0.1 to about 3 g/m² by using coatingsolutions containing between about 0.5 and about 8 percent by weight ofthe dye-releaser distributed in a hydrophilic film-forming naturalmaterial or synthetic polymer, such as gelatin, polyvinyl alcohol, etc,which is adapted to be permeated by aqueous alkaline processingcomposition.

Depending upon which CAR is used in the present invention, a variety ofsilver halide developing agents or electron transfer agents (ETA's) areuseful in this invention. In certain embodiments of the invention, anyETA can be employed as long as it cross-oxidizes with the dye-releasersdescribed herein. The ETA may also be incorporated in the photosensitiveelement to be activated by the alkaline processing composition. Specificexamples of ETA's useful in this invention include hydroquinonecompounds, such as hydroquinone, 2,5-dichlorohydroquinone or2-chlorohydroquinone; aminophenol compounds, such as 4-aminophenol,N-methylaminophenol, N,N-dimethylaminophenol, 3-methyl-4-aminophenol or3,5-dibromoaminophenol; catechol compounds, such as catechol,4-cyclohexylcatechol, 3-methoxycatechol or 4-(N-octadecylamino)catechol;and phenylenediamine compounds, such asN,N,N',N'-tetramethyl-p-phenylenediamine. In highly preferredembodiments, the ETA is a 3-pyrazolidinone compound, such as1-phenyl-3-pyrazolidinone (Phenidone),1-phenyl-4,4-dimethyl-3-pyrazolidinone (Dimezone),4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone,4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone,4-hydroxymethyl-4-methyl-1-(3,4-dimethylphenyl)-3-pyrazolidinone,1-m-tolyl-3-pyrazolidinone, 1-p-tolyl-3-pyrazolidinone,1-phenyl-4-methyl-3-pyrazolidinone, 1-phenyl-5-methyl-3-pyrazolidinone,1-phenyl-4,4-dihydroxymethyl-3-pyrazolidinone,1,4-dimethyl-3-pyrazolidinone, 4-methyl-3-pyrazolidinone,4,4-dimethyl-3-pyrazolidinone,1-(3-chlorophenyl)-4-methyl-3-pyrazolidinone,1-(4-chlorophenyl)-4-methyl-3-pyrazolidinone,1-(3-chlorophenyl)-3-pyrazolidinone,1-(4-chlorophenyl)-3-pyrazolidinone,1-(4-tolyl)-4-methyl-3-pyrazolidinone,1-(2-tolyl)-4-methyl-3-pyrazolidinone, 1-(4-tolyl)-3-pyrazolidinone,1-(3-tolyl)-3-pyrazolidinone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidinone,1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidinone or5-methyl-3-pyrazolidinone. A combination of different ETA's, such asthose disclosed in U.S. Pat. No. 3,039,869, can also be employed. TheseETA's are employed in the liquid processing composition or contained, atleast in part, in any layer or layers of the photographic element orfilm unit to be activated by the alkaline processing composition, suchas in the silver halide emulsion layers, the dye image-providingmaterial layers, interlayers, image-receiving layer, etc.

In a preferred embodiment of the invention, the silver halide developerof ETA employed in the process becomes oxidized upon development andreduces silver halide to silver metal. The oxidized developer thancross-oxidizes the dye-releasing compound. The product ofcross-oxidation then undergoes alkaline hydrolysis, thus releasing animagewise distribution of diffusible azo dye which then diffuses to thereceiving layer to provide the dye image. The diffusible moiety istransferable in alkaline processing composition either by virtue of itsself-diffusivity or by its having attached to it one or moresolubilizing groups, for example, a carboxy, sulpho, sulphonamido,hydroxy or morpholino group.

In using the dye-releasing compounds according to the invention whichproduce diffusible dye images as a function of development, eitherconventional negative-working or direct-positive silver halide emulsionsare employed. If the silver halide emulsion employed is adirect-positive silver halide emulsion, such as an internal-imageemulsion designed for use in the internal image reversal process or afogged, direct-positive emulsion such as a solarizing emulsion, which isdevelopable in unexposed areas, a positive image can be obtained incertain embodiments on the dye image-receiving layer. After exposure ofthe film unit, the alkaline processing composition permeates the variouslayers to initiate development of the exposed photosensitive silverhalide emulsion layers. The developing agent present in the film unitdevelops each of the silver halide emulsion layers in the unexposedareas (since the silver halide emulsions are direct-positive ones), thuscausing the developing agent to become oxidized imagewise correspondingto the unexposed areas of the direct-positive silver halide emulsionlayers. The oxidized developing agent then crossoxidizes thedye-releasing compounds and the oxidized form of the compounds thenundergoes a base-catalyzed reaction to release the dyes imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers. At least a portion of the imagewise distributions of diffusibledyes diffuse to the image-receiving layer to form a positive image ofthe original subject. After being contacted by the alkaline processingcomposition, a neutralizing layer in the film unit or image-receivingunit lowers the pH of the film unit or image receiver to stabilize theimage.

Internal-image silver halide emulsions useful in this invention aredescribed more fully in the November 1976 edition of ResearchDisclosure, pages 76 through 79, the disclosure of which is herebyincorporated by reference.

The various silver halide emulsion layers of a color film assemblyemployed in this invention are disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a yellowcolloidal silver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layers for absorbing or filteringblue radiation that is transmitted through the blue-sensitive layer. Ifdesired, the selectively sensitized silver halide emulsion layers can bedisposed in a different order, e.g., the blue-sensitive layer first withrespect to the exposure side, followed by the red-sensitive andgreen-sensitive layers.

The rupturable container employed in certain embodiments of thisinvention is disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886;3,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. In general,such containers comprise a rectangular sheet of fluid- andair-impervious material folded longitudinally upon itself to form twowalls which are sealed to one another along their longitudinal and endmargins to form a cavity in which processing solution is contained.

Generally speaking, except where noted otherwise, the silver halideemulsion layers employed in the invention comprise photosensitive silverhalide dispersed in gelatin and are about 0.6 to 6 microns in thickness;the dye-releasers are dispersed in an aqueous alkalinesolution-permeable polymeric binder, such as gelatin, as a separatelayer about 0.2 to 7 microns in thickness; and the alkalinesolution-permeable polymeric interlayers, e.g., gelatin, are about 0.2to 5 microns in thickness. Of course, these thicknesses are approximateonly and can be modified according to the product desired.

Scavengers for oxidized developing agent can be employed in variousinterlayers of the photographic elements of the invention. Suitablematerials are disclosed on page 83 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Any material is useful as the image-receiving layer in this invention aslong as the desired function of mordanting or otherwise fixing the dyeimages is obtained. The particular material chosen will, of course,depend upon the dye to be mordanted. Suitable materials are disclosed onpages 80 through 82 of the November 1976 edition of Research Disclosure,the disclosure of which is hereby incorporated by reference.

Use of a neutralizing material in the film units employed in thisinvention will usually increase the stability of the transferred image.Generally, the neutralizing material will effect a reduction in the pHof the image layer from about 13 or 14 to at least 11 and preferably 5to 8 within a short time after imbibition. Suitable materials and theirfunctioning are disclosed on pages 22 and 23 of the July 1974 edition ofResearch Disclosure, and pages 35 through 37 of the July 1975 edition ofResearch Disclosure, the disclosures of which are hereby incorporated byreference.

A timing or inert spacer layer can be employed in the practice of thisinvention over the neutralizing layer which "times" or controls the pHreduction as a function of the rate at which alkali diffuses through theinert spacer layer. Examples of such timing layer and their functioningare disclosed in the Research Disclosure articles mentioned in theparagraph above concerning neutralizing layers.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., alkalimetal hydroxides or carbonates such as sodium hydroxide, sodiumcarbonate or an amine such as diethylamine, preferably possessing a pHin excess of 11, and preferably containing a developing agent asdescribed previously. Suitable materials and addenda frequently added tosuch compositions are disclosed on pages 79 and 80 of the November 1976edition of Research Disclosure, the disclosure of which is herebyincorporated by reference.

The alkaline solution-permeable, substantially opaque, light-reflectivelayer employed in certain embodiments of photographic film units used inthis invention is described more fully in the November 1976 edition ofResearch Disclosure, page 82, the disclosure of which is herebyincorporated by reference.

The supports for the photographic elements used in this invention can beany material as long as it does not deleteriously affect thephotographic properties of the film unit and is dimensionally stable.Typical flexible sheet materials are described on page 85 of theNovember 1976 edition of Research Disclosure, the disclosure of which ishereby incorporated by reference.

While the invention has been described with reference to layers ofsilver halide emulsions and dye image-providing materials, dotwisecoating, such as would be obtained using a gravure printing technique,could also be employed. In this technique, small dots of blue-, green-and red-sensitive emulsions have associated therewith, respectively,dots of yellow, magenta and cyan color-providing substances. Afterdevelopment, the transferred dyes would tend to fuse together into acontinuous tone. In an alternative embodiment, the emulsions sensitiveto each of three primary regions of the spectrum can be disposed as asingle segmented layer, e.g., as by the use of microvessels as describedin Whitmore U.S. Patent Application Ser. No. 184,714, filed Sept. 8,1980.

The silver halide emulsions useful in this invention, bothnegative-working and direct-positive ones, are well known to thoseskilled in the art and are described in Research Disclosure, Volume 176,December 1978, Item No. 17643, pages 22 and 23, "Emulsion preparationand types"; they are usually chemically and spectrally sensitized asdescribed on page 23, "Chemical sensitization", and "Spectralsensitization and desensitization", of the above article; they areoptionally protected against the production of fog and stabilizedagainst loss of sensitivity during keeping by employing the materialsdescribed on pages 24 and 25, "Antifoggants and stabilizers", of theabove article; they usually contain hardeners and coating aids asdescribed on page 26, "Hardeners", and pages 26 and 27, "Coating aids",of the above article; they and other layers in the photographic elementsused in this invention usually contain plasticizers, vehicles and filterdyes described on page 27, "Plasticizers and lubricants"; page 26,"Vehicles and vehicle extenders" ; and pages 25 and 26, "Absorbing andscattering materials", of the above article; they and other layers inthe photographic elements used in this invention can contain addendawhich are incorporated by using the procedures described on page 27,"Methods of addition", of the above article; and they are usually coatedand dried by using the various techniques described on pages 27 and 28,"Coating and drying procedures", of the above article, the disclosuresof which are hereby incorporated by reference.

The term "nondiffusing" used herein has the meaning commonly applied tothe term in photography and denotes materials that, for all practicalpurposes, do not migrate or wander through organic colloid layers, suchas gelatin, in the photographic elements of the invention in an alkalinemedium and preferably when processed in a medium having a pH of 11 orgreater. The same meaning is to be attached to the term "immobile". Theterm "diffusible" as applied to the materials of this invention has theconverse meaning and denotes materials having the property of diffusingeffectively through the colloid layers of the photographic elements inan alkaline medium. "Mobile" has the same meaning as "diffusible".

The term "associated therewith" as used herein is intended to mean thatthe materials can be in either the same or different layers, so long asthe materials are accessible to one another.

The following examples are provided to further illustrate the invention.

EXAMPLE 1 Hue Test--Released Dyes

A receiving element was prepared comprising a poly(ethyleneterephthalate) film support having thereon a nickel sulfate hexahydrate(0.58 g/m²)-gelatin (1.08 g/m²) metal complexing layer, and apoly(4-vinylpyridine)-gelatin mordant layer (each at 2.15 g/m²).

The receiving element was immersed in an alkaline solution of the azodyes listed in the Table below. The receiver was removed from the dyesolution, washed in distilled water, placed in a pH 7.0 buffer solutionand dried. Transmission spectra obtained on each sample were normalizedto a density of 1.0. The λ_(max) at maximum density, along with the"half band width" (1/2 BW), the wavelength range of the curve at halfthe maximum density, and the λ 1/2, the center of the wavelength rangeat half the maximum density, are recorded in the Table below. A narrow1/2 BW generally designates a pure hue. With respect to those dyes whichhave two distinct maxima, the highest density λ_(max) is given first.

A fading test was also run wherein the samples were mounted on aperturecards and subjected to 5000-foot-candle Xenon arc radiation (HighIntensity Daylight or HID) for 10 and 21 days using a Wratten 2B filter.The curves were run against an undyed receiver as a reference. Thepercentage of dye left at each time interval was measured and recordedin the Table below.

                                      TABLE                                       __________________________________________________________________________     ##STR17##                                                                                                               Dye Stability                                                      Hue (nm)                                                                             pH 7                                                                              10 (21) Day HID                    Cmpd.                                                                             R.sup.4                                                                            R.sup.3                                                                            R.sup.2                                                                           R.sup.1                                                                          E    M     λ.sub.1/2                                                                 (HBW)                                                                             λ.sub.max                                                                  % Dye Left                         __________________________________________________________________________    A   (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                     H    H     538                                                                              (95)                                                                              533,563                                                                           82  (71)                           B   H   CH.sub.3                                                                            (CH.sub.2).sub.3                                                                     H    SO.sub.2 NH.sub.2                                                                   544                                                                              (78)                                                                              561 91  (85)                           C   (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                     H    SO.sub.2 NH.sub.2                                                                   551                                                                              (82)                                                                              569 87                                 D   (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                     3-Cl SO.sub.2 NH.sub.2                                                                   551                                                                              (79)                                                                              562 95  (88)                           E   (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                     3-CH.sub.3                                                                         SO.sub.2 NH.sub.2                                                                   553                                                                              (88)                                                                              570 90  (83)                           F   (CH.sub.2).sub.3                                                                        (CH.sub.2).sub.3                                                                     3-OCH.sub.3                                                                        SO.sub.2 NH.sub.2                                                                   567                                                                              (95)                                                                              565 91  (85)                           G   CHOHCH.sub.2                                                                            CH.sub.3                                                                          H  H    SO.sub.2 NH.sub.2                                                                   537                                                                              (87)                                                                              562,530                                                                           94  (90)                           H   CHOHCH.sub.2                                                                            CH.sub.3                                                                          H  3-CH.sub.3                                                                         SO.sub.2 NH.sub.2                                                                   546                                                                              (93)                                                                              574,539                                                                           95  (91)                           I   CHOHCH.sub.2                                                                            CH.sub.3                                                                          H  3-Cl SO.sub.2 NH.sub.2                                                                   540                                                                              (91)                                                                              561,538                                                                           94  (89)                           J   CHOHCH.sub.2                                                                            CH.sub.3                                                                          H  3-OCH.sub.3                                                                        SO.sub.2 NH.sub.2                                                                   555                                                                              (100)                                                                             585,550                                                                           95  (90)                           __________________________________________________________________________

The above results illustrate that the dyes of our invention have aparticularly good magenta hue having spectra with narrow halfbandwidths. They also have good light stability.

Synthetic Procedures

The azojulolidinol dyes of the invention, such as Compounds A, C, D, E,and F of the preceeding Table, were prepared from 8-julolidinol byoxidation with Fremy's salt, potassium nitrosodisulfonate, NO(SO₃ K)₂,to the 8,9-quinone which then on reaction with the appropriatelysubstituted 2-pyridylhydrazine gave the azo dye. Alternatively, the8-julolidinol can be nitrosated, the nitroso group hydrogenated, and theresulting aminophenol air-oxidized to the quinone. The latter procedurewas used for preparing Compound C.

Tetrahydroazoquinolinol dyes of the invention can be prepared accordingto the following sequence for Compound B: ##STR18## The dyes derivedfrom adrenochrome (Compounds G, H, I and J) were prepared from adrenalinaccording to the following sequence for Compound H: ##STR19##

EXAMPLE 2 Preparation of Compound 4

A mixture of 9-nitroso-8-julolidinol (1.9 g), sodium acetate (0.8 g), 5percent palladium on charcoal catalyst (0.1 g), and 12 ml acetic acidwas hydrogenated at 42 p.s.i. at room temperature for 2 hours. Themixture was filtered and the residue was washed with 5 ml of aceticacid. Two drops of water were added to the filtrate and then air wasbubbled through the filtrate for 1 hour. Then it was added to4-(3-chloro-2-hydrazino-5-pyridinesulfonamido)-1-hydroxy-N,N-dioctadecyl-2-naphthamide(3.2 g) which had been dissolved in 15 ml hot acetic acid and thencooled preceding the addition. The mixture was stirred at roomtemperature for 68 hours and filtered to give 3.0 g of crude product.The product was combined with that of another run and the total (5.1 g)was dissolved in methylene chloride and chromatographed on Grade 62,60-200 mesh silica gel. Impurities were removed with 1-2 percent acetonein methylene chloride and then the product was eluted with 5 percentacetone in methylene chloride. The eluates were concentrated to an oilwhich was slurried in ethanol to give 1.7 g of product. The product wasrecrystallized from 40 ml ethyl acetate to give 1.4 g product, m.p.134°-6° C., .sup.ε 557=5.66×10⁴ in 3/1:Dioxane/water in the presence ofNi⁺⁺ ion.

Intermediates

A.4-(3-Chloro-2-hydrazino-5-pyridinesulfonamido)-1-hydroxy-N,N-dioctadecyl-2-naphthamide

A mixture of 25.3 g (0.0276 mole)4-(2,3-dichloro-5-pyridine-sulfonamido)-1-hydroxy-N,N-dioctadecyl-2-naphthamide,8.9 g 95 percent hydrazine and 795 ml methanol was heated under refluxfor 17.5 hours and chilled. The precipitate was filtered off, washedwith cold ethanol and then with water and air dried to give 24.2 g (96percent) product, m.p. 75°-7° C. TLC on Eastman Chromagram™ silica gelsheets with fluorescent indicator using an 85/15 mixture of methylenechloride/acetone indicated slight impurities.

B.4-(2,3-Dichloro-5-pyridinesulfonamido)-1-hydroxy-N,N-dioctadecyl-2-naphthamide

A solution of 22.5 g (0.0318 mole)4-amino-1-hydroxy-N,N-dioctadecyl-2-naphthamide and 4.0 g (0.5 mole)pyridine in 300 ml tetrahydrofuran (THF) under nitrogen was stirred atroom temperature and a solution of 9.0 g (0.036 mole)2,3-dichloropyridine-5-sulfonyl chloride in 50 ml THF was added. Themixture was stirred 2 hours at room temperature. A thin-layer Chromogramon silica gel sheets indicated unreacted amine, so an additional 1.0 gof the sulfonyl chloride was added followed by 0.5 ml pyridine andstirring for an additional hour. Since a thin-layer chromotogramindicated no more amine, the mixture was concentrated to a small volumeon a rotary evaporator, slurried in water several times with the waterlayer decanted off each time. The oil was dissolved in ether, water wasseparated, and the extract was dried with anhydrous Na₂ SO₄. The etherlayer was removed to leave a reddish oil which solidified on standing.The oil was extracted several times with boiling acetonitrile to leave apurplish black residue. The extracts were chilled and the precipitatewas reextracted; chilling the extracts gave 25.7 g (88 percent) ofproduct as a beige powder with a m.p. 88°-9° C.

C. 9-Nitrosojulolidinol hydrochloride

A solution of 10.0 g (0.0528 mole) 8-julolidinol in 120 ml MeOHpreviously saturated with HCl gas was stirred with a magnetic stirrerand chilled below 10° C. in an ice/water bath. Fairly rapidly 6.5 g(0.055 mole) isopentyl nitrite was dripped in. After the addition themixture became too thick to stir with the magnetic stirrer. The mixturewas allowed to stand 20 minutes in the ice/water bath and was thenfiltered. The solid was washed with a little cold MeOH and then withseveral portions of ether and air dried to give 11.4 g (85 percent) ofproduct as an orange solid, dec. 153° C.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A nondiffusible compound having a releasablemagenta dye moiety or precursor thereof, said compound having theformula: ##STR20## wherein: (a) R represents hydrogen, a hydrolyzablemoiety or CAR;(b) R¹ represents hydrogen; (c) R² represents an alkylgroup of 1 to about 6 carbon atoms or CAR; or R¹ and R² represent analkylene group which can be taken together with the atoms to which theyare attached to complete a 5- or 6-membered heterocyclic ring; (d) R³represents an alkyl group of 1 to about 6 carbon atoms or CAR; (e) R⁴represents hydrogen; or R³ and R⁴ represent an alkylene group which canbe taken together with the atoms to which they are attached to completea 5- or 6-membered heterocyclic ring;with the proviso that at least oneof said 5- or 6-membered heterocyclic rings of (c) or (e) is present insaid compound; (f) CAR represents a ballasted carrier moiety capable ofreleasing said diffusible magenta dye moiety or precursor thereof underalkaline conditions; and (g) n is 0, 1 or 2, with the proviso that whenn is 0, then at least one of R, R² or R³ is CAR.
 2. The compound ofclaim 1 wherein R represents hydrogen, R¹ and R² complete a 6-memberedheterocyclic ring, R³ and R⁴ complete a 6-membered heterocyclic ring andn is
 1. 3. The compound of claim 1 wherein R represents hydrogen, R¹ andR² complete a 6-membered heterocyclic ring, R³ represents methyl, R⁴represents hydrogen and n is
 1. 4. The compound of claim 1 wherein Rrepresents hydrogen, R¹ represents hydrogen, R² represents methyl, R³and R⁴ complete a 5-membered heterocyclic ring and n is
 1. 5. Thecompound of claim 1 wherein CAR is a group having the formula:

    (Ballast-Carrier-Link)--

wherein: (a) Ballast is an organic ballasting radical of such molecularsize and configuration as to render said compound nondiffusible in aphotographic element during development in an alkaline processingcomposition; (b) Carrier is an oxidizable acyclic, carbocyclic orheterocyclic moiety; and (c) Link represents a group which, uponoxidation of said carrier moiety, is capable of being hydrolyticallycleaved to release said diffusible dye.
 6. The compound of claim 5wherein the Carrier moiety contains atoms according to the followingconfiguration:

    a (--C═C).sub.b --

wherein: b is a positive integer of 1 to 2; and a represents theradicals OH, SH, NH-- or hydrolyzable precursors thereof.
 7. Thecompound of claim 1 wherein CAR is a group having the formula: ##STR21##wherein: (a) Ballast is an organic ballasting radical of such molecularsize and configuration as to render said compound nondiffusible in aphotographic element during development in an alkaline processingcomposition;(b) D is OR⁵ or NHR⁶ wherein R⁵ is hydrogen or ahydrolyzable moiety and R⁶ is hydrogen or a substituted or unsubstitutedalkyl group of 1 to 22 carbon atoms; (c) Y represents the atomsnecessary to complete a benzene nucleus, a naphthalene nucleus, or a 5to 7 membered heterocyclic ring; and (d) j is a positive integer of 1 to2 and is 2 when D is OR⁵ or when R⁶ is hydrogen or an alkyl group ofless than 8 carbon atoms.
 8. The compound of claim 7 wherein D is OH, jis 2 and Y is a naphthalene nucleus.
 9. The compound of claim 1 whereinsaid CAR is capable of releasing said diffusible bridged, azoaminophenolmagenta dye moiety or precursor thereof as an inverse function ofdevelopment of a silver halide emulsion layer under alkaline conditions.10. The compound of claim 9 wherein said CAR is a group having theformula: ##STR22## wherein: Ballast is an organic ballasting radical ofsuch molecular size and configuration as to render said compoundnondiffusible in a photographic element during said development in analkaline processing composition;W¹ represents at least the atomsnecessary to complete a quinone nucleus; r is a positive integer of 1 or2; R⁷ is an alkyl radical having 1 to about 40 carbon atoms or an arylradical having 6 to about 40 carbon atoms; and k is a positive integerof 1 to 2 and is 2 when R⁷ is a radical of less than 8 carbon atoms. 11.The compound of claim 9 wherein said CAR is a group having the formula:##STR23## wherein: Ballast is an organic ballasting radical of suchmolecular size and configuration as to render said compoundnondiffusible in a photographic element during said development in analkaline processing composition;W² represents at least the atomsnecessary to complete a benzene nucleus; and R⁸ is an alkyl radicalhaving 1 to about 4 carbon atoms.
 12. The compound of claim 9 whereinsaid CAR is a group having the formula: ##STR24## wherein: Ballast is anorganic ballasting radical of such molecular size and configuration asto render said compound nondiffusible in a photographic element duringsaid development in an alkaline processing composition;W² represents atleast the atoms necessary to complete a benzene nucleus; and R⁸ is analkyl radical having 1 to about 4 carbon atoms.
 13. The compound ofclaim 9 wherein said CAR is a group having the formula: ##STR25##wherein: Ballast is an organic ballasting radical of such molecular sizeand configuration as to render said compound nondiffusible in aphotographic element during said development in an alkaline processingcomposition;W² represents at least the atoms necessary to complete abenzene nucleus; r is a positive integer of 1 or 2; R⁷ is an alkylradical having 1 to about 40 carbon atoms or an aryl radical having 6 toabout 40 carbon atoms; k is a positive integer of 1 to 2 and is 2 whenR⁷ is a radical of less than 8 carbon atoms; and K is OH or ahydrolyzable precursor thereof.
 14. The compound of claim 1 wherein saiddye-releasing compound is: ##STR26##